Silicone modified acrylics and epoxies

ABSTRACT

The present invention includes a novel polyol prepolmer including either an aliphatic amine, cycloaliphatic amine, aromatic amine or a mixture of these with an epoxy functional silicone to produce the novel polyol prepolymer chain extender. In one aspect of the invention, the novel polyol prepolymer chain extender is reacted with an epoxy resin to produce a novel silicone modified epoxy resin having improved adhesion, chemical resistance, UV stability, and decreased shrinkage properties. In another aspect of the invention, the novel polyol prepolymer chain extender is reacted with an acrylic monomer to produce a novel silicone modified acrylic resin having improved adhesion, chemical resistance, UV stability, increased functionality, and decreased shrinkage properties. The present invention also provides for a novel solid surface material composition.

CROSS-REFERENCES TO RELATED APPLICATIONS

[0001] This application is a continuation-in-part of application Ser.No. 10/648,934 filed 27 Aug. 2003 which claims the benefit of U.S.Provisional Application No. 60/408,797 filed 9 Sep. 2002 and U.S.Provisional Application No. 60/412,211 filed 23 Sep. 2002.

FIELD OF THE INVENTION

[0002] The present invention relates to synthetic resins and processesfor making the same and more particularly, relates to methods andcompositions for making aliphatic and aromatic two part polyureaelastomers, acrylics, and epoxies having improved adhesion, chemicalresistance, UV stability, and decreased shrinkage properties.

Problem

[0003] Conventional epoxy resins mean generally a thermosetting resinformed originally by the polymerization of bisphenol A andepicholorohydrin based on the reactivity of the epoxide group. Mostepoxy resins are the two-part type which hardens when blended.Generally, epoxy resins make great adhesives, and are one of the fewadhesives that can be used on metals. They're also used for applicationslike protective coatings, and as materials in products like electroniccircuit boards and for patching holes in concrete pavement.

[0004] Epoxy resins can be formulated with different materials orblended with other epoxy resins to achieve specific performancefeatures. Cure rates can be controlled to match process requirementsthrough the proper selection of hardeners and/or catalyst systems.Generally, epoxies are cured by addition of an anhydride or an aminehardener as a two-part system. Different hardeners, as well as quantityof a hardener produce a different cure profile and give differentproperties to the finished composite.

[0005] Typical epoxy resin formulas do not however, have particularlygood UV resistance. Since the viscosity of epoxy is much higher thanmost polyester resin, typical epoxy resin formulas are slow to cure andrequire a post-cure (elevated temperature) to obtain ultimate mechanicalproperties making epoxies more difficult to use. Others problems withtypical epoxy resin formulas include brittleness and decreasedflexibility when finished to a cured film. Also, typical epoxy resinformulas are not very mar or graffiti resistant and possess averageadhesion properties. In addition, typical epoxy resin formulas have afunctionality of two due to the available crosslinking sites.

[0006] Like epoxy resins, acrylic resins are also very useful in termsof adhesive properties and chemical resistance properties. In the formof solutions, acrylic resins serve as fixatives, picture varnishes,paints, synthetic rubber, and lightweight plastics, and in the form ofwater emulsions, as binders for prepared artist's tempera. Acrylicresins can be unaffected by alkalis, hydrocarbons, non-oxidizing acids,saltwater, and photographic or battery solutions. Acrylic resins alsomake outstanding coatings for large metal structures, such as ships andbridges. Acrylic resins are typically mixed from dry powder acrylicpolymers, methyl methacrylate monomers, and usually an organic peroxidehardener of some sort.

[0007] Acrylic resins are also used to make materials, such as solidsurface materials. Typically, to produce a solid surface material, suchas culture marble or granite mix, unsaturated polyesters and peroxidesare mixed together with granite mixes of different colors. A typicalformula would include 100 PBW of unsaturated polyesters, 2% Methyl EthylKetone Peroxide (peroxide catalyst), and 300 PBW granite mix. Thecharacteristics of this typical formula include a gel time of 45 minutesand a cure time of 4-6 hours. Typical solid surface material does nothave a high gloss and can not withstand high impact when dropped.Further, typical solid surface material formulas are flammable, meaningwhen they are subjected to high heat sources, such as propane torches,they burn and give off black smoke. Another problem of typical solidsurface material formulas are that the formulas comprises 40% styrenemonomers, which is an emission that the EPA regulates, and thus requiresstringent operating conditions to conform to environmental standards.Yet another problem of solid surface material made with conventionalformulas including unsaturated polyesters and peroxides, is that thematerial generally has a strong styrene monomer odor after curing andmars very easily.

[0008] Conventional polyurea coatings typically possess severalcharacteristics that have made them desirable as a seamless membraneincluding fast, consistent reactivity and cure, moisture and temperatureinsensitivity during application, exceptional elastomeric quality,hydrolytically stable (i.e. low water absorption), high thermalstability, and that they are auto catalytic and do not emit solvents orVOC's when applied. However, many characteristics of conventionalpolyureas are unfavorable and limit their use in many applications.

[0009] The conventional aromatic polyurea uses mixtures of aromaticdiamines such as diethyltoluenediamine and polyether amines reacted withan methylene diphenyl isocyanate (MDI) prepolymer with optional levelsof propylene carbonate added. This material reacts in 5 seconds toproduce a polyurea. A conventional aliphatic polyurea can be made withaliphatic isocyanate reacted with aliphatic amines, such as JeffamineT-403, D400, D2000 from Huntsman or NH 1220 and NH 1420 from Bayer. Thisreaction is very fast with gel times of 5 seconds. Both the conventionalaromatic and aliphatic polyureas are attacked by strong solvents such asxylene, toluene, acetone, low pH acids, and high pH caustics.

[0010] Another undesirable characteristics of conventional polyureas isthat conventional polyureas possess poor adhesion properties.Specifically, the fast reaction times inherent in conventional polyureascut short the time needed for a conventional polyurea to penetrate andadhere to its substrate. Commercial epoxy type resins have been used inplace of conventional polyureas because they are slow to react butpenetrate to give excellent adhesion and chemical resistance.

[0011] Yet another problem of conventional polyureas and epoxies is thatthey do not possess good color stability or UV resistance. Aromaticpolyureas, due to their aromatic reactants, generally turn yellow orbrown when exposed to ultraviolet (UV) light and oxygen. Since polyureascan be formulated in a variety of colors, this discoloration traitadversely affects the intended finish color of the conventionalpolyurea, especially in light colors. Also, conventional polyureasshrink about 1%-1.5% when they cure, which means, for example, when1,000 linear feet of polyurea is applied to a roofing project, once itcures, some 10 to 15 feet of polyurea will shrink and need to bereapplied.

[0012] Information relevant to attempts to address these problems can befound in the U.S. Pat. No. 5,731,397 issued 24 Mar. 1998 to Primeaux andU.S. Pat. No. 5,962,618 issued 5 Oct. 1999 to Primeaux.

[0013] Therefore, there is a need for epoxy resins and acrylic resinswith a silicone backbone that would increase chemical resistance, UVstability, adhesion, and decreased shrinkage properties. Furthermore,there is a need for epoxy resins and acrylic resins that are notsusceptible to non-homogeneous mixtures that provide epoxy resins andacrylic resins in differing consistencies and properties.

Solution

[0014] The above described problems are solved and a technical advanceachieved in the art by a polyol prepolymer chain extender with aliphaticepoxy end groups that can react with either an aliphatic amine, anaromatic amine, a cycloaliphatic amine or a combination of these. Thepolyol prepolymer chain extender is then mixed with epoxy resinreactants to form silicone modified epoxy resins, which significantlyimproves the characteristic of the epoxy resin. In another aspect, thepolyol prepolymer chain extender is mixed with a multi-functionalacrylic monomer to form silicone modified acrylic resins.

[0015] The polyol prepolymer chain extender can be either aliphatic,aromatic, cycloaliphatic or any combination of these. The polyolprepolymer chain extender is preferably prepared prior to mixing witheither the epoxy resin or the multi-functional acrylic monomer. Byreacting an epoxy silicone with a primary amine, epoxy and acrylicresins are produced which include a silicone backbone for improvedproperties.

[0016] The novel polyol prepolymer chain extenders produce epoxies andacrylics with improved characteristics, such as improved UV stabilityand resistance, improved adhesion, excellent chemical and marresistance, better flow, elongation improvement, hardening, improvedgraffiti resistance, and improved impact resistance.

[0017] In addition, solid surface material formulas prepared with thenovel polyol prepolymer chain extenders have higher gloss finish, bettergel and cure times, improved mar resistance, better flame resistance,and greater impact resistance. Further, these improved solid surfacematerial formulas are able to accommodate higher concentrations ofgranite mix, while remaining fluid.

DETAILED DESCRIPTION OF THE INVENTION

[0018] Polyureas typically have A-component reactants and B-componentreactants that are kept in separate containers or vessels, due to theirreactivity, and are mixed just prior to being applied to a substrate.Conventionally, the A-component reactants include a polyisocyanate andthe B-component reactants include an amine terminated polyol.

[0019] The present invention B-component reactants include a novelpolyol prepolymer chain extender that includes at least one aminereacted with an epoxy functional silicone. In one aspect of the presentinvention, the polyol prepolymer chain extender includes a silicone thathas an epoxy end group which reacts with an aromatic or aliphatic amineor combination of aromatic and aliphatic amines to produce the novelpolyol prepolymer chain extender. In one aspect of the presentinvention, the epoxy end group on the silicone is aliphatic and morepreferably is glycidyl ether. The aliphatic epoxy end group providesincreased UV and color stability of the silicone modified polyurea.Exemplary epoxy functional silicones include 2810 from OSI Specialtiesand SILRES© HP 1000 from Wacker Chemicals Corp. Both products haveHydrogen equivalent weights of 300-400. One non-limiting example of anepoxy functional silicone is shown in formula (I):

[0020] The amines of the B-component polyol prepolymer chain extenderpreferably include primary and secondary amines reacted with the epoxyfunctional silicone. In one aspect of the polyol prepolymer chainextender, the aliphatic primary amines are low molecular weight amines,such as D230, D400, or T403 from Huntsman, polyaspartic amines, such asNH 1220 and NH 1420 from Bayer, and dimethylthiotoluenediamine (DMTDA),3,5-dimethylthio-2,6-toluenediamine or3,5-dimethylthio-2,4-toluenediamine, such as E-300 from AlbermarleCorporation. In addition, aromatic amines may be used in the polyolprepolymer chain extender, such as diethyltoluenediamine (DETDA) E-100Ethacure from Albemarle Corporation. In one aspect of the present polyolprepolymer chain extender, these amines are used in combination with oneanother or separately, when reacted with an epoxy functional silicone.The gel and tack free time for the two component silicone modifiedpolyurea can be adjusted by using different combinations and amounts ofthese amines with the epoxy functional silicone during the preparationof the polyol prepolymer chain extender. For example to produce asilicone modified polyurea with fast gel and tack free time, a polyolprepolymer chain extender is prepared including D400 and E-100 which isreacted with an epoxy functional silicone prior to mixing with thepolyisocyanate. Conversely, for slower gel and tack free time, a polyolprepolymer chain extender is prepared including NH1220 and D400 which isreacted with an epoxy functional silicone. Some non-limiting examples ofthe aliphatic primary amines are shown in formulas (II), (III), and(IV):

[0021] The following chart shows the hydrogen equivalent weights of somethese non-limiting aliphatic primary amines. Equivalent/gm Equivalent/gmProduct for Epoxy for Urea T-403 80 115 D-400 115 230 D-230 60 115

[0022] In addition to the novel polyol prepolymer chain extender hereindescribed, the B-component of the present silicone modified polyureaalso preferably includes high molecular weight amine-terminatedpolyethers or simply polyether amines. The term “high molecular weight”is intended to include polyether amines having a molecular weight of atleast about 2000. Particularly preferred are the JEFFAMINE® series ofpolyether amines available from Huntsman Corporation; they includeJEFFAMINE D-2000, JEFFAMINE D4000, JEFFAMINE T-3000 and JEFFAMINET-5000.

[0023] In addition, the B-component of the silicone modified polyureaalso preferably includes addition amounts of curative amines, such asE-100 Ethacure from Albermarle. Also preferably, aromatic diamines, suchas Unilink 4200 from UOP, which is a secondary amine, are added to theB-component to help control the cross-linking and reactivity of thesilicone modified polyurea.

[0024] In addition, the B-component preferably includes at least onecoupling agent, such as A1100 (amino propyl silane). The coupling agentis typically a silane with amine on the end of it so it become reactiveas part of the structure. Other coupling agents that can be used areglycidylether silane, such as A-187 from OSi Specialties, Inc., which isa polyglyceride.

[0025] Also, pigments, for example titanium dioxide, may be incorporatedin the B-component, to impart color properties to the silicone modifiedpolyurea. Typically, such pigments are added with the in the B-componentprior to mixing with the A-component. A non-limiting example of atitanium dioxide pigment is Ti-Pure ® R-900 rutile titanium dioxide fromE.I. DuPont de Nemours Co.

[0026] In addition, UV stabilizer materials are also preferably mixedwith the B-components, to impart better UV resistance to the siliconemodified polyurea. Some non-limiting examples of UV stabilizers areTinuvin ® 328 and Tinuvin ® 765 from Ciba-Geigy Corp.

[0027] The aliphatic and/or aromatic silicone modified polyurea of thepresent invention typically includes an A-component, such as anisocyanate, which may be an aliphatic or aromatic isocyanate. Thealiphatic isocyanates are known to those in the art. For instance, thealiphatic isocyanates may be of the type described in U.S. Pat. No.4,748,192, incorporated by reference herein. Accordingly, they aretypically aliphatic diisocyanates, and more particularly are thetrimerized or the biuretic form of an aliphatic diisocyanate, such as,hexamethylene diisocyanate (HMDI); or the bifunctional monomer of thetetraalkyl xylene diisocyanate, such as tetramethyl xylene diisocyanate(TMXDI). Cyclohexane diisocyanate is also to be considered a preferredaliphatic isocyanate. Other useful aliphatic polyisocyanates aredescribed in U.S. Pat. No. 4,705,814, also incorporated by referenceherein. They include aliphatic diisocyanate, for example, alkylenediisocyanate with 4 to 12 carbon atoms in the alkylene radical, such as1,12-dodecane diisocyanate and 1,4-tetramethylene diisocyanate. Alsodescribed are cycloaliphatic diisocyanates, such as 1,3- and1,4-cyclohexane diisocyanate as well as any desired mixture of theseisomers; 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane(isophorone diisocyanate); 4,4′-, 2,2′- and 2,4′-dicyclohexylmethanediisocyanate, as well as the corresponding isomer mixtures, and thelike. Exemplary isocyanate monomers include monoisocyanate compound(p=1) such as m- or p-isopropenyl-α, α dimethylbenzoyl isocyanate.

[0028] Aromatic isocyanates may also be employed. Suitable aromaticpolyisocyanates include, but are not necessarily limited to m-phenylenediisocyanate; p-phenylene diisocyanate; polymethylene polyphenylenediisocyanate; 2,4-toluene diisocyanate; 2-6 toluene diisocyanate;dianisidine diisocyanate, bitolylene diisocyanate;naphthalene-1,4-diisocyanate; diphenylene 4,4′-diisocyanate and thelike. Suitable aliphatic/aromatic diisocyantes, include, but are notnecessarily limited to xylylene-1,3-diisocyanate,bis(4-isocyanatophenyl)methane; bis(3-methyl-4-isocyanatophenyl)methane;and 4,4′-diphenylpropane diisocyanate. The aforestated isocyanates canbe used alone or in combination. In one embodiment of the invention,aromatic isocyanates are preferred.

[0029] The isocyanate compound used in the present invention has astructure wherein all of the isocyanate (NCO) groups in the moleculehave secondary or tertiary carbon bonded thereto. The groups other thanthe NCO group bonding to the secondary or the tertiary carbon are notlimited, for example, in terms of the number of carbon atoms, bulkiness,inclusion of hetero atoms such as O, S, and N, and the like. The twogroups bonding to the tertiary carbon may be either the same ordifferent from each other.

[0030] When producing a polyol prepolymer chain extender or anisocyanate prepolymer, it is necessary have to have an adduct or excessamount of amine to keep the reactants liquid. This also means that theadduct or excess of amine reacts with the isocyanate prepolymer whenmaking the final silicone modified polyurea. This requires carefullyadjusting of the amine level, so that the speed of reactivity andconversion are controlled. Therefore, when mixing an A-component and aB-component together, it is preferable to include 105%stoichiometrically of the A-component compared to the B-component. Thismeans a 5% stoichimetric excess of polyisocyanates are preferably usedin the mixtures. This is done because any excess isocyanate willmoisture cure.

[0031] This careful attention to the amine adduct is also importantduring application to a substrate, such as spraying. The viscosity ofthe mix at the tip of the application device, such as an impingementgun, is very important, because if the viscosity is too high then theinternal mix with the A-component reactants and the B-componentreactants is inadequate for a consistent silicone modified polyurea.Furthermore, if the viscosity is too high, then additional heat may berequired to raise the temperatures of the reactants to bring theviscosity down low enough to spray.

[0032] Three non-limiting examples of the novel polyol prepolymer chainextender are shown in formulas (V), (VI), and (VII):

[0033] where the values of W, X, Y, and Z in formulas (V), (VI), and(VII) are as follows. The value for X is a number greater than or equalto 1, and preferably X is in the range of from 1 to 10, and morepreferably, X is equal to 1. The value for Z is a number greater than orequal to 1. The value for Y is a number greater than or equal to 1, andpreferably Y is in the range or from 10-200, and more preferably Y isbetween 5 and 7. The value for W is a number greater than or equal to 1.

[0034] Two non-limiting examples of the novel silicone modified polyureaare shown in formulas (VIII) and (IX):

[0035] where R, R′, and R″ groups are the novel polyol prepolymer chainextenders described herein.

[0036] The following examples are provided to further illustrate thepreferred embodiments of the present invention polyol prepolymer chainextender, but should not be construed as limiting the invention in anyway. Compositions of the polyol prepolymer chain extender were producedby mixing amines with an epoxy functional silicone polymer shown inExamples 1-7. The following amines were reacted with the followingsilicone polymers noted in Table 1. TABLE 1 Examples 1 2 3 4 5 6 7 T-403300 — — — — — — 2810 or HP1000 100 100 100 100 100 100 100 D400 — 300300 — — 300 300 E-100 — — 500 — 500 — — D230 — — — 300 300 — — E-300 — —— — — 500 — NH1220 — — — — — — 400

[0037] All amounts of the compounds in Table 1 are represented by partsby weight. The reactions between the amines and the epoxy functionalsilicone polymer are slow and produce a low exotherm. In one aspect ofthe present invention, to increase reaction times of these reactants inExamples 1-7, the reactants are heated to a minimum temperature from130° F. to 210° F., preferably 180° F., for two hours with an excess ofamine to keep the product liquid, as provided in the Table 1. In anotheraspect of the present invention, the heating periods are between 30minutes to 24 hours. In one aspect of the present invention the polyolprepolymer chain extender was allowed to cool prior to mixing with otherreactants, described herein, in the B-component formula. In anotheraspect of the present invention, all reactants of the B-componentformula, described herein, are mixed together and heated from 130° F. to210° F., preferably 180° F., for a minimum of 30 minutes. The excessamount of amine can be adjusted to suit the purpose of a specificapplication. It is understood that increased amounts of silicone arebetter for polyurea performance. The polyisocyanate is preferablyprepared using a 2000 molecular weight (mwt) silicone diol reacted withan isocyanate to form a polyurea prepolymer with better chemical and UVresistance when its product is reacted to the silicone modified polyolside. Silicone 2812 from OSI is a 2000 mwt diol with 1000 eq. Wt.Examples of the prepolymer are as follows in Examples 8-9.

EXAMPLE 8

[0038] A 22% NCO aliphatic dimer such as N-3400 (Bayer) is reacted with2812 (OSI) silicone at a ratio of: 80 PBW N3400 20 PBW 2812

[0039] All amounts are represented by parts by weight. This product isheated at 150° F. for two hours. The results are an 18% NCO polyureaprepolymer with silicone in the backbone.

EXAMPLE 9

[0040] A 29% NCO aromatic urethane isocyanate, ICI Huntsman 1680, isreacted with 2812 silicone at a ratio of: 60 PBW 1680 40 PBW 2812

[0041] All amounts are represented by parts by weight. This product washeated at 180° F. for two hours. The result is a 16% NCO polyureaprepolymer with silicone in the backbone.

[0042] Examples of silicone modified polyureas are given below inExamples 10-15.

EXAXPLE 10 Aliphatic Silicone Polyurea

[0043] An aliphatic silicone modified polyurea was prepared with 15 PBWT-403/2810 adduct (Example 1), 75 PBW NH1220 (Bayer) polyaspartic ester,10. PBW pigment white (TiO₂), 1 PBW T-292 UV stabilizer, and 0.8 PBWA1100 silane coupling agent. This constitutes the B-component of thealiphatic silicone modified polyurea. This was mixed to 110 PBW ofpolyurea prepolymer of Example 8. This aliphatic silicone modifiedpolyurea has a gel time of about 45 seconds when spray applied by aGusmer H2035 spray machine. The product was spray applied to a concreteand metal panel and checked for adhesion and placed in a weathermeterfor UV stability.

EXAMPLE 11 Another Aliphatic Polyurea without Silicone

[0044] An aliphatic modified polyurea was prepared with 15 PBW T-403, 75PBW NH1220 (Bayer) polyaspartic ester, 10 PBW pigment white (TiO₂), 1PBW T-292 UV stabilizer, and 18 PBW A1100 silane coupling agent. Thisconstitutes the B-component of the aliphatic modified polyurea. This wasmixed to 110 PBW of polyurea prepolymer consisting of N3400 and D2000Jeffamines mixed to 18% NCO. This aliphatic modified polyurea has a geltime of approximately 15 seconds when spray applied by a Gusmer H2035spray machine. The product was spray applied to a concrete and metalpanel and checked for adhesion and placed in a weathermeter for UVstability.

EXAMPLE 12 Aromatic Polyurea

[0045] An aromatic polyurea was prepared with 15 PBW E-100diethyltoluenediamine (DETDA), 10 PBW D400, and 75 PBW D2000. Thisconstitutes the B-component of the aromatic silicone modified polyurea.This was mixed to 110 PBW of polyurea prepolymer consisting of aHuntsman 9484 prepolymer MDI with 16% NCO. This aromatic siliconemodified polyurea has a gel time of approximately 5 seconds when sprayapplied by a Gusmer H2035 spray machine. The product was spray appliedto a concrete and metal panel and checked for adhesion and placed in aweathermeter for UV stability.

EXAMPLE 13 Aromatic Polyurea with Silicone

[0046] An aromatic silicone modified polyurea was prepared with 25 PBWD400/2810/E-100 (Example 3), 75 PBW D2000. This constitutes theB-component of the aromatic silicone modified polyurea. This was mixedto 110 PBW of polyurea prepolymer consisting of a Huntsman 9484prepolymer MDI with 16% NCO. This has a gel time of approximately 10seconds when spray applied by a Gusmer H2035 spray machine. The productwas spray applied to a concrete and metal panel and checked for adhesionand placed in a weathermeter for UV stability.

EXAMPLE 14 Another Aromatic Polyurea with Silicone

[0047] An aromatic silicone modified polyurea with silicone was preparedwith 15 PBW E-100 diethyltoluenediamine (DETDA), 10 PBW D400/2810 adduct(Example 2), and 75 PBW D2000. This constitutes the B-component of thearomatic silicone polyurea. This was mixed to 110 PBW of polyureaprepolymer of 29% NCO aromatic urethane isocyanate (Example 9). Thisaromatic silicone modified polyurea has a gel time of approximately 8seconds when spray applied by a Gusmer H2035 spray machine. The productwas spray applied to a concrete and metal panel and checked for adhesionand placed in a weathermeter for UV stability.

EXAMPLE 15 Another Aromatic Polyurea with Silicone

[0048] An aromatic silicone modified polyurea with silicone was preparedwith 25 PBW E-100/D400/HP1000 (Example 3), 75 PBW D2000. Thisconstitutes the B-component of the aromatic silicone modified polyurea.This was mixed to 110 PBW of polyurea prepolymer of 29% NCO aromaticurethane isocyanate (Example 9). This aromatic silicone modifiedpolyurea has a gel time of approximately 12 seconds when spray appliedby a Gusmer H2035 spray machine. The product was spray applied to aconcrete and metal panel and checked for adhesion and placed in aweathermeter for UV stability.

[0049] The compositions of Examples 10-15 were evaluated and are shownin Table 2. TABLE 2 Adhesion PSI Examples Concrete Steel UV Results in1000 Hrs 10 400 1200 Excellent 11 309 1000 Slight Yellow 12 350 1250Yellow/Brownish 13 400 1275 Yellow 14 450 1375 Slight Yellow 15 475 1400Very Slight Yellow

[0050] The above UV results were achieved by using a B-bulb on a QUVmachine. Also the adhesion results were performed using ASTM #4551elcometer. The adducts in which E-100, silicone, and polyether aminethat were pre-heated show better adhesion and UV resistance then whenE-100 is added without being reacted.

[0051] The compositions of Examples 10-15 were evaluated for chemicalresistance and are shown in Table 3. TABLE 3 H₂SO₄ H₂PO₄ Examples XyleneToluene Acetone MEK (50%) HCl (50%) (50%) Caustic 10 R R R R R R R R 11RC RC RC NR NR NR NR NR 12 RC RC RC NR NR NR NR NR 13 RC RC RC NR NR NRNR NR 14 R R R R R R R R 15 R R R R R R R R

[0052] All samples in Table 3 were placed in a glass cover for 48 hourswith the chemical on the surface of the sample. R=Recommended,RC=Recommended conditional, NR=Not recommended

[0053] Additional examples of silicone modified polyureas are givenbelow. Comparative examples 16-18 are conventional ratios andcompositions and do not include any polyol prepoymer. Examples 19-20 areexamples of the present silicone modified polyurea and do includeamounts of different combinations and ratios of the novel polyolprepolymer chain extenders.

COMPARATIVE EXAMPLES 16-17AND EXAMPLES 18-20

[0054] TABLE 4 Examples 16 17 18 19 20 Polyol prepolymer chain — — — —25 extender of Example 3 D2000 (Jeffamine) 50 50 45 45 45 T-5000(Jeffamine) 10 10 10 — — Polyol prepolymer chain — — — 10 10 extender ofExample 7 E100 (Ethacure) 25 15 15 15 — 4200 (Unilink) — 10 — — — A-1870.4 0.4 0.4 0.4 0.4 15.5% NCO Index 105 105 105 105 105 Gel Time (Sec)3.5 4.8 5.0 4.5 4.5 Tack Free (Sec) 5.5 7.5 7.5 6.5 7.5

Physical Property Testing

[0055] Physical property testing for the silicone modified polyureasnoted in Table 4 were done in accordance with American Society forTesting and Materials (ASTM). The ASTM test methods and their physicalproperty test descriptions are given below in Table 5: TABLE 5 Examples16 17 18 19 20 Tensile Strength PSI 2541 2430 2516 3350 3620 ASTM D-638% Elongation 235 265 410 340 300 ASTM D-638 Tear Strength P.L.I. 357 340500 525 610 ASTM D-624 Shore Hardness D 47/40 47/40 47/40 47/40 50/45ASTM D2240-81 Abrasion HS-18 Wheel 0.6 0.6 0.4 0.4 0.4 (mg) 1000 gm -1000 cycle loss ASTM D-4060 Elcometer PSI — — — — — Concrete 450 375 750900 950 Steel >1000 >1000 >1300 >1500 >1500 ASTM 4551 Moisture Vapor<0.1 <0.1 <0.1 <0.1 <0.1 Transmission (Perms) ASTM E96-80 WaterAbsorption (%) 1.90 2.20 1.25 0.85 0.85 WT Gain ASTM D570-95

[0056] Additional examples of silicone modified polyureas are givenbelow. Comparative examples 21-22 are conventional ratios andcompositions and do not include any polyol prepolymer. Examples 23-24are examples of the present silicone modified polyurea and do includeamounts of different combinations and ratios of the novel polyolprepolymer chain extenders.

COMPARATIVE EXAMPLES 21-22 AND EXAMPLES 23-24

[0057] TABLE 6 Examples 21 22 23 24 D2000 (Jeffamine) 50 50 45 45 T-5000(Jeffamine) 10 10 10 — Polyol prepolymer chain — — 10 — extender ofExample 7 Polyol prepolymer chain — — — 25 extender of Example 6 E100(Ethacure) 25 15 15 — 4200 (Unilink) — 10 — — A-187 0.4 0.4 0.4 0.415.5% NCO Index 105 105 105 105 Gel Time (Sec) 3.5 4.8 5.0 35.0 TackFree (Sec) 5.5 7.5 7.5 50.0

Physical Property Testing

[0058] Physical property testing for the silicone modified polyureasnoted in Table 6 were done in accordance with American Society forTesting and Materials (ASTM). The ASTM test methods and their physicalproperty test descriptions are given below in Table 7: TABLE 7 Examples21 22 23 24 Tensile Strength PSI 2541 2430 2516 3350 ASTM D-638 %Elongation  235  265  410  340 ASTM D-638 Tear Strength P.L.I.  357  340 500  525 ASTM D-624 Shore Hardness D 47/40 47/40 47/40 47/40 ASTMD2240-81 Abrasion HS-18 Wheel 0.6 mg 0.6 mg 0.4 mg 0.4 mg 1000 gm —1000cycle loss loss loss loss ASTM D-4060 Elcometer PSI — — — — Concrete 450  375  750  900 Steel >1000  >1000  >1300  >1500  ASTM 4551 MoistureVapor    <0.1    <0.1    <0.1    <0.1 Transmission (Perms) ASTM E96-80Water Absorption 1.90% 2.20% 1.25% 0.85% WT Gain ASTM D570-95

[0059] Additional examples of silicone modified polyureas are givenbelow. Comparative examples 25-26 are conventional ratios andcompositions and do not include any polyol prepoymer. Examples 27-28 areexamples of the present silicone modified polyurea and do includeamounts of different combinations and ratios of the novel polyolprepolymer chain extenders.

COMPARATIVE EXAMPLES 25-26 AND EXAMPLES 27-28

[0060] TABLE 8 Examples 25 26 27 28 D2000 (Jeffamine) 50 50 45 45 T-5000(Jeffamine) 10 10 10 — Polyol prepolymer chain — — 10 — extender ofExample 7 E100 (Ethacure) 25 15 15 — 4200 (Unilink) — 10 — — A-187 0.40.4 0.4 0.4 15.5% NCO Index 105 105 105 105 Gel Time (Sec) 3.5 4.8 5.035.0 Tack Free (Sec) 5.5 7.5 7.5 50.0

Physical Property Testing

[0061] Physical property testing for the silicone modified polyureasnoted in Table 8 were done in accordance with American Society forTesting and Materials (ASTM). The ASTM test methods and their physicalproperty test descriptions are given below in Table 9: TABLE 9 Examples23 24 25 26 Tensile Strength PSI 2541 2430 2720 3610 ASTM D-638 %Elongation  235  265  420  350 ASTM D-638 Tear Strength P.L.I.  357  340 510  550 ASTM D-624 Shore Hardness D 47/40 47/40 47/40 47/40 ASTMD2240-81 Abrasion HS-18 Wheel 0.6 mg 0.6 mg 0.4 mg 0.4 mg 1000 gm —1000cycle loss loss loss loss ASTM D-4060 Elcometer PSI — — — — Concrete 450  375  750  900 Steel >1000  >1000  >1300  >1500  ASTM 4551 MoistureVapor    <0.1    <0.1    <0.1    <0.1 Transmission (Perms) ASTM E96-80Water Absorption 1.90% 2.20% 1.25% 0.85% WT Gain ASTM D570-95

[0062] In addition to that disclosed above, the novel polyol prepolymerchain extenders can be used as chain extenders for other types ofreactions to produce acrylics, epoxies, and other materials.

[0063] In one aspect of the present invention, the novel polyolprepolymer includes reacting an epoxy functional silicone with an amine,such as an aliphatic, aromatic, cycloaliphatic amines, or combinationsof these. In addition, mixtures of different aliphatic amines may bereacted with an epoxy functional silicone to produce the novel polyolprepolymer. Exemplary cycloaliphatic amines include3-aminomethyl-3,5,5-trimethylcyclohexylamine (also known asisophoronediamine or IPDA), 1,3-Bis(aminomethyl)benzene (also known asmetaxylylenediamine or MXDA), and 1,2-Diaminocyclohexane, such as Dytek®DCH-99 from Invista. Exemplary aromatic amines includediethyltoluenediamine (DETDA) E-100 Ethacure anddimethylthiotoluenediamine (DMTDA), 3,5-dimethylthio-2,6-toluenediamineor 3,5-dimethylthio-2,4-toluenediamine, such as E-300 from AlbermarleCorporation. An exemplary aliphatic amine includes2-Methylpentamethylenediamine (MPMD), such as Dytek® A Amine fromDuPont. Several non-limiting examples of the aliphatic andcycloaliphatic amines are shown in formulas (X), (XI), (XII), and(XIII):

[0064] The aliphatic and cycloaliphatic amines are mixed with an epoxyfunctional silicones such as SILRES® HP 1000 at a weight ratio of 3:1amine to silicone. Blends of these reacted silicone amines may also bemade to alter the epoxy's properties when reacted with the epoxy resins.

[0065] Exemplary epoxy resins include diglycidyl ether of bisphenol Aepoxy resin, such as Shell EPON 828 epoxy resin and bisphenol F epoxyresin. One non-limiting example of an epoxy resin is shown in formula(XIV):

[0066] wherein n is preferably between 1 and 25.

[0067] The following examples are provided to further illustrate thepreferred embodiments of the present invention polyol prepolymer chainextender, but should not be construed as limiting the invention in anyway. Compositions of the polyol prepolymer chain extender were producedby mixing the aliphatic and cycloaliphatic amines with an epoxyfunctional silicone polymer shown in Examples 27-30. The followingamines were reacted with the following silicone polymers to create thefollowing novel polyol prepolymer chain extenders noted in Table 10.TABLE 10 Examples 27 28 29 30 IPDA 300 — — — MXDA — 300 — —1,2-Diaminocyclohexane — — 300 — MPMD — — — 300 HP 1000 100 100 100 100

[0068] All amounts of the compounds in Table 10 are represented by partsby weight. The reactants are heated to a temperature of 200° F. for 2hours.

[0069] Examples of silicone modified epoxies are given below in Examples31-34. Comparative example 35 does not include any polyol prepolymer.The following Examples of silicone modified epoxies are given below inTable 11. TABLE 11 Examples 31 32 33 34 35 Polyol prepolymer chain 50 —— — — extender of Example 27 Polyol prepolymer chain — 50 — — — extenderof Example 28 Polyol prepolymer chain — — 50 — — extender of Example 29Polyol prepolymer chain — — — 50 — extender of Example 30 IPDA — — — —35 Epoxy 828 100  100  100  100  100  Gel time (Min) 30 35 39 40 40 TackFree (Hrs)  4  5  4  5  5

[0070] All amounts of the compounds in Table 11 are represented by partsby weight. Examples 31 and 35 were placed 16 millimeters on a steelpanel and allowed to dry. After 24 hours the samples were tested foradhesion to metal and film integrity. Adhesion results were performedusing ASTM # 4551 elcometer.

[0071] After the 24 hour period, Example 31 was fully cured andexhibited 850 PSI on the elcometer pull test. The film was high in glossand showed excellent mar resistance. Conversely, after the 24 hourperiod, Example 35 was not fully cured, 15 marred easily, and exhibited400 PSI on the elcometer pull test. Also, importantly, the functionalityof the silicone hardener becomes 6 from 2 increasing the crosslinkdensity of the epoxy, which increases the chemical resistance of thesilicone modified epoxies. The functionality of these polyol prepolymersincreases from 2 to 6 for the aliphatic diamines and to 9 with thealiphatic triamines. Examples 32-34 showed similar results to Example31.

[0072] Additional examples of silicone modified epoxies are given belowin Examples 36-39. The following Examples of silicone modified epoxiesare given below in Table 12. TABLE 12 Examples 36 37 38 39 Polyolprepolymer chain — — 60 — extender of Example 1 Polyol prepolymer chain— — — 20 extender of Example 2 Polyol prepolymer chain 50 50 — 40extender of Example 4 Acrylic Oligomer* 20 — 20 — Coatosil 1211**  1  1 1  1 Benzyl Alcohol — 20 — 20 Epoxy 190 EqWT 80 80 80 80 Gel time (Min)35 45 35 60 Tack Free (Hrs)  4  4  4  8

[0073] Generally, the Jeffamine materials are slower reacting withepoxies and the Dytek® materials, such as 1,2-Diaminocyclohexane and2-Methylpentamethylenediamine, are generally faster reacting withepoxies. To achieve a particular speed of reaction with the epoxies,mixtures of the Jeffamines and the Dytek® materials are combined. Forexample, IPDA is mixed at a ratio of 3:1 with HP 1000 and then mixed ata ratio of 1:1 with the novel polyol prepolymers of Examples 1, 2, or 4.In another example, TETA is mixed at a ratio of 3:1 with HP 1000 andthen mixed at a ratio of 1:1 with the novel polyol prepolymers ofExamples 1, 2, or 4. The addition of the epoxy functional siliconeimproves the hydrophobic and weatherability properties of the epoxies.

[0074] In addition, aliphatic amines, such as polyether amines incombination with the cycloaliphatic amines are mixed with epoxies toproduce additional silicone modified epoxies. Examples 40-44 of thesemixtures of amines are given below in Examples 40-44 in Table 13. TABLE13 Examples 40 41 42 43 44 D230 10 — — — 10 D400 — 10 — — — T403 — — 1010 — T-5000 (Jeffamine) — — — 5 5 IPDA 30 30 30 30 30 MXDA — — — — —1,2-Diaminocyclohexane — — — — — MPMD — — — — — Epoxy 828 100 100 100100 100 Functionality 2 2 3 3 2.5 Gel Time (Min) 35 50 30 35 35 TackFree (Hrs) 4 8 4 5 4.5

[0075] All amounts of the compounds in Table 13 are represented by partsby weight. These results show that incorporation of the polyether amineof higher molecular weight combined with the cycloaliphatic amine whenreacted with an epoxy resin provide a silicone modified epoxy withimproved flexibility to the finish cured film and decreases brittlenesstypical of other epoxy mixes. Further, all samples still showed a highgloss, excellent adhesion, mar resistance, and excellent UV stabilityand chemical resistance properties.

[0076] The selection of the aliphatic or cycloaliphatic amine to bemixed with the epoxy functional silicone is determined by the desiredcharacteristics of the epoxy and its application.

[0077] In another aspect of the present invention, the novel polyolprepolymer chain extenders produce acrylic resins with improvedcharacteristics. In this aspect, the novel polyol prepolymer is reactedwith an acrylic monomer, to form an acrylic polymer. Preferably, theseacrylic monomers are multi-functional such as trimethylolpropanetriacrylate (TMPTA) and pentaerythritol triacrylate (PETA). Othernon-limiting examples of multi-functional monomers include propoxylated(6) trimethylolpropane triacrylate, highly propoxylated (5.5) glyceryltriacrylate, methacrylate ester, trimethylolpropane trimethacrylate, lowviscosity trimethylolpropane triacrylate, tris(2-hydroxy ethyl)isocyanurate triacrylate, ethoxylated (20) trimethylolpropanetriacrylate, ethoxylated (3) trimethylolpropane triacrylate,propoxylated (3) trimethylolpropane triacrylate, ethoxylated (6)trimethylolpropane acrylate, ethoxylated (9) trimethylolpropaneacrylate, propoxylated (3) glyceryl triacrylate, and ethoxylated (15)trimethylolpropane triacrylate. Some non-limiting examples of thesemulti-functional acrylic monomers are shown in formulas (XV) and (XVI):

[0078] The following examples are provided to further illustrate thepreferred embodiments of the present invention polyol prepolymer chainextender, but should not be construed as limiting the invention in anyway. The composition of the polyol prepolymer chain extender used inExample 29 is reacted with the following multi-functional acrylicmonomers to produce silicone modified acrylics. Some examples of thesesilicone modified acrylics are given below in Examples 45-47 in Table14. TABLE 14 Examples 45 46 47 Polyol prepolymer chain 50 50 50 extenderof Example 29 TMPTA 100 — 30 PETA — 100 50 Gel time (Sec) 600 5 300

[0079] All amounts of the compounds in Table 14 are represented by partsby weight. In addition to these mixtures, additional mixtures of theseamines may be 15 mixed with an epoxy functional silicone to produce thenovel polyol prepolymer chain extenders. For example, IPDA is mixed at a3:1 ratio with HP 1000 and then this mixture is mixed in equal partswith 2-Methylpentamethylenediamine. In another example,tetraethyltriamine (TETA) is mixed with the epoxy functional silicone.The present invention provides for these amines to mixed with the epoxyfunctional silicone individually or these amines may be mixed togetherand then mixed at a general ratio of 3:1 to the epoxy functionalsilicone. All samples were clear and had exotherm of 200° F. in 100 grammass. A 4″ disc was cast for each sample and all samples cured to ashore of 80 for hardness.

[0080] In another aspect of the present invention, these siliconemodified acrylics are used to produce materials, such as solid surfacematerial, with improved characteristics.

[0081] The following examples are provided to further illustrate thepreferred embodiments of the present invention polyol prepolymer chainextender, but should not be construed as limiting the invention in anyway. The composition of the polyol prepolymer chain extender used inExample 29 is reacted with the following multi-functional acrylicmonomers and granite mixes to produce improved solid surface materials.Comparative Example 54 is a conventional composition of solid surfacematerial that does not include the polyol prepolymer. Examples of theseimproved solid surface materials are given below in Examples 48-54 inTable 15. TABLE 15 Examples 48 49 50 51 52 53 54 Polyol prepolymer 50 5050 — — — — chain extender of Example 29 3:1 IPDA/HP 1000 — — — 50 — — —3:1 MXDA/HP 1000 — — — — 30 — — MPMD — — — — — 50 — TMPTA 100  — 30 100 100  30 — PETA — 100  50 — — 50 — Unsaturated — — — — — — 100 polyesters Mek P (peroxide — — — — — —  2 catalyst), % Granite mix 300 300  300  300  300  300  300  Gel time (Min) 15  7 10  9 12 11 60 Curetime (Min) 30 15 20 30 30 20 6-8 Hrs.

[0082] All amounts of the compounds in Table 15 are represented by partsby weight, unless otherwise noted. Examples 48-53 had a high gloss andhigh impact when dropped. Example 54 broke on impact. Further, there wasno odor to Examples 48-53 after curing, however, Example 54 had a strongstyrene monomer smell after curing. In addition, Examples 48-53 weresubjected to a propane torch and showed no smoke and just formed a blackchar. Example 54 was subjected to a propane torch and the sample burnedand gave off black smoke. Furthermore, Examples 48-53 possessed good marresistance, whereas Example 54 marred very easily. The gel time and curetime for Examples 51 and 52 were slightly faster than Examples 48-50.Further, when additional filler amounts of granite, such as 400 PBW,were added to Examples 48-53 the silicone modified acrylic resinsremained fluid, with lower surface tension, but when this additionalamount of granite was added to Example 54, the unsaturated polyestersample became too dry and the unsaturated polyester in unable to wet thefiller.

Spray Application

[0083] In one aspect of the present invention, a method is included forapplying the present invention silicone modified polyurea to asubstrate, and more specifically, applying to concrete or steel.

[0084] For preparation of old concrete prior to application,sandblasting, shot blasting, or water blasting is highly preferable toremove any surface contaminates. Any oils or fats should be removedprior to application of the silicone modified polyurea. Acid etching maybe required (followed by a thorough rinsing) to open the pores of theconcrete to accept a primer coat. A primer may be applied, such asReactamine® Primer from Reactamine Technologies, LLC, to further improvethe bonding of the silicone modified polyurea to the concrete. A minimum40-mil coating is generally preferable for improved chemical andabrasion resistance.

[0085] For preparation of new concrete, the concrete should cure forpreferably a minimum of 30 days. Also preferably, sand blasting, shotblasting, or acid etching (15% muriatic acid/85% water) is required toremove the surface lattice that appeared during the curing process.Again, a primer, such as Reactamine® Primer, is preferably applied toreduce out gassing of the concrete.

[0086] For preparation of steel, the steel must be prepared to a “nearwhite metal” equivalent to SSPC 10 or NACE 2 standards. For immersionservice, a 3-mil blast profile is preferable. A 2-mil blast profile isgenerally recommended. A 10-40 mil coat of Reactamine® Primer isgenerally preferable for improved chemical resistance performance.

[0087] In one aspect, the present invention includes the following sprayapplication. A substrate (concrete, steel, etc.) is preferably preparedas described herein. In one aspect, the B-component is contained in onecontainer and the A-component is contained in another. Into each ofthese two containers is placed a displacement pump connected to a hose.The respective displacement pump pumps the respective component storedin that container through the respective hose to a separate volumetriccylinder-type measurement devices, which accurately measures the exactamounts of the A-component and B-component. The A-component is measuredin one volumetric cylinder-type measurement device and the B-componentis measured in another. Preferably, each cylinder measures equal Eachvolumetric cylinder-type measurement device is then pressurized in therange from 500 psi to 3000 psi. The A-component and the B-component arethen separately pumped through a heater which heats each componentseparately to temperatures from about 50° F. to 250° F. The separatedindividual components are then pumped through one heated hose for eachcomponent and sent to an impingement spray gun.

[0088] For example, the present invention silicone modified polyurea ispreferably applied to the substrate using a high pressure pluralcomponent pump (1:1 by volume), such as a GlasCraft-MX® equipped with aProber® impingement mix spray gun or a Gusmer® H-20/35 proportioningunit and a Gusmer® GX-7 (400 Series) or GX-8 impingement mix spray gun.As described above, each proportioning unit is preferably capable ofsupplying the correct pressure and heat for the required hose length ona consistent basis. In addition, the hose is preferably heated to keepthe reactants at a temperature of at least 150° F. Preferably, forprocessing, the block temperature of the heater was set at 160° F. forboth the B-component and the A-component and the hose temperature wasset at 160° F. for both components. Processing was at 2500 psig staticpressure and 2000 psig spray pressure.

Summary

[0089] There has been described a novel polyol prepolymer chain extenderand silicone modified epoxy and acrylic resins that can be aliphatic. Itshould be understood that the particular embodiments described withinthis specification are for purposes of example and should not beconstrued to limit the invention. Further, it is evident that thoseskilled in the art may now make numerous uses and modifications of thespecific embodiment described, without departing from the inventiveconcepts. It is also evident that the process steps recited may in someinstances be performed in a different order, or equivalent structuresand processes may be substituted for the various structures andprocesses described. The structures and processes may be combined with awide variety of other structures and processes.

Glossary

[0090] ETHACURE ® 100 Diethyltoluene diamine chain extender availablefrom Albemarle™ Corporation.

[0091] JEFFAMINE ® D-2000 A 2000 molecular weight polyoxypropylenediamine available from Huntsman Petrochemical Corporation.

[0092] JEFFAMINE ® T-5000 A 5000 molecular weight polyoxypropylenetriamine available from Huntsman Petrochemical Corporation.

[0093] SILQUEST ® A-187 Functional alkoxy silane available from OSiSpecialties, Inc./Crompton Corp.

[0094] UNILINK® 4200 Dialkyl substituted methylene dianiline chainextender available from UOP Chemical Co.

[0095] Tinuvin® 328 UV stabilizer available from Ciba-Geigy Corp.

[0096] Tinuvin® 765 UV stabilizer available from Ciba-Geigy Corp.

[0097] Ti-Pure® R-900 Rutile titanium dioxide available from E.I. DuPontde Nemours Co.

[0098] Silquest® A-1100 Gamma-aminopropyltriethoxysilane is anamino-functional coupling agent from OSi Specialties, Inc./CromptonCorp.

[0099] MDI 1680 4,4-Diphenylisocyanate from Huntsman Petrochemical Corp.

[0100] N-3400 1,6-Hexamethylenediisocanate.

[0101] CoatOSil® 2810 Epoxy silicone copolymers similar to HP 1000.

[0102] OSi 2812 2000 mwt silicone endcapped diol.

[0103] NH1220 and NH1420 Polyaspartic esters from Bayer.

[0104] AFL-5 and AFL-10 Aminofunctional poly-dimethylsiloxanes

[0105] IPDI Isophorone di-isocyanate

[0106] HDI Hexamethyl di-isocyanate

[0107] TMXDI Tetramethyl xylene di-isocyante

[0108] Rubinate® 9484 MDI Methylene diphenyl isocyanate from HuntsmanPetrochemical Corp.

What is claimed:
 1. A polyol prepolymer chain extender for siliconemodified epoxies and silicone modified acrylics comprising: at least oneamine; and at least one epoxy functional silicone.
 2. The polyolprepolymer chain extender of claim 1 wherein said at least one amine isselected from the group consisting of primary aliphatic amines, aromaticamines, primary cycloaliphatic amines, secondary aliphatic amines, andmixtures thereof.
 3. The polyol prepolymer chain extender of claim 1wherein said epoxy functional silicone is a silicone modified epoxyresin that has the general formula:


4. The polyol prepolymer chain extender of claim 1 wherein said at leastone amine is present in the range of from about 50 to about 900 parts byweight, based on the total polyol prepolymer chain extender.
 5. Thepolyol prepolymer chain extender of claim 1 wherein said at least oneepoxy functional silicone is present in the range of from about 10 toabout 300 parts by weight, based on the total polyol prepolymer chainextender.
 6. The polyol prepolymer chain extender of claim 1 whereinsaid at least one amine is a cycloaliphatic amine that has the generalformula:


7. The polyol prepolymer chain extender of claim 1 wherein said at leastone amine is a cycloaliphatic amine that has the general formula:


8. The polyol prepolymer chain extender of claim 1 wherein said at leastone amine is a cylcoaliphatic amine that has the general formula:


9. The polyol prepolymer chain extender of claim 1 wherein said at leastone amine is an aliphatic amine that has the general formula:


10. A silicone modified epoxy resin comprising: a first component whichincludes at least one polyol prepolymer chain extender which comprises:at least one amine; at least one epoxy functional silicone; and a secondcomponent which comprises at least one epoxy resin.
 11. The siliconemodified epoxy resin of claim 10 wherein said at least one amine isselected from the group consisting of primary aliphatic amines, aromaticamines, primary cycloaliphatic amines, secondary aliphatic amines, or acombination of said amines.
 12. The silicone modified epoxy resin ofclaim 10 wherein said epoxy functional silicone is a silicone modifiedepoxy resin that has the general formula:


13. The silicone modified epoxy resin of claim 10 wherein said epoxyresin has the general formula:


14. The silicone modified epoxy resin of claim 10 wherein said epoxyresin is selected from the group consisting of diglycidyl ether ofbisphenol A and bisphenol F epoxy resin; and mixtures thereof.
 15. Thesilicone modified epoxy resin of claim 10 wherein said polyol prepolymerchain extender is present in the range of from about 10 to about 100parts by weight, based on the total silicone modified epoxy resin. 16.The silicone modified epoxy resin of claim 10 wherein said at least oneepoxy resin is present in the range of from about 50 to about 200 partsby weight, based on the total silicone modified epoxy resin.
 17. Thesilicone modified epoxy resin of claim 10 wherein said second componentfurther comprises UV stabilizers.
 18. The silicone modified epoxy resinof claim 10, further comprising color pigments.
 19. The siliconemodified epoxy resin of claim 10 wherein said first component furthercomprises silane coupling agents.
 20. The silicone modified epoxy resinof claim 10, further comprising fire retardants.
 21. A silicone modifiedacrylic resin comprising: a first component which includes at least onepolyol prepolymer chain extender which comprises: at least one amine; atleast one epoxy functional silicone; and a second component whichcomprises at least one acrylic monomer.
 22. The silicone modifiedacrylic resin of claim 21 wherein said at least one acrylic monomer ismulti-functional.
 23. The silicone modified acrylic resin of claim 21wherein said at least one amine is selected from the group consisting ofprimary aliphatic amines, primary cycloaliphatic amines, secondaryaliphatic amines, or a combination of said amines.
 24. The siliconemodified acrylic resin of claim 21 wherein said epoxy functionalsilicone is a silicone modified epoxy resin that has the generalformula:


25. The silicone modified epoxy resin of claim 21 wherein said acrylicmonomer is selected from the group consisting of trimethylolpropanetriacrylate, pentaerythritol triacrylate, propoxylated (6)trimethylolpropane triacrylate, highly propoxylated (5.5) glyceryltriacrylate, methacrylate ester, trimethylolpropane trimethacrylate, lowviscosity trimethylolpropane triacrylate, tris (2-hydroxy ethyl)isocyanurate triacrylate, ethoxylated (20) trimethylolpropanetriacrylate, ethoxylated (3) trimethylolpropane triacrylate,propoxylated (3) trimethylolpropane triacrylate, ethoxylated (6)trimethylolpropane acrylate, ethoxylated (9) trimethylolpropaneacrylate, propoxylated (3) glyceryl triacrylate, and ethoxylated (15)trimethylolpropane triacrylate; and mixtures thereof.
 26. The siliconemodified acrylic resin of claim 21 wherein said polyol prepolymer chainextender is present in the range of from about 10 to about 100 parts byweight, based on the total silicone modified acrylic resin.
 27. Thesilicone modified acrylic resin of claim 21 wherein said at least onacrylic monomer is present in the range of from about 20 to about 200parts by weight, based on the total silicone modified acrylic resin. 28.The silicone modified acrylic resin of claim 21 wherein said firstcomponent further comprises UV stabilizers.
 29. The silicone modifiedacrylic resin of claim 21 wherein said first component further comprisescolor pigments.
 30. The silicone modified acrylic resin of claim 21wherein said first component further comprises silane coupling agents.31. The silicone modified acrylic resin of claim 21 wherein said firstcomponent further comprises fire retardants.
 32. A solid surfacematerial composition comprising: a first component which includes atleast one polyol prepolymer chain extender which comprises: at least oneamine; at least one epoxy functional silicone; a second component whichcomprises at least one acrylic monomer; and a granite mix.
 33. The solidsurface material composition of claim 32 wherein said polyol prepolymeris present in the range of from about 10 to about 100 parts by weight,based on the total solid surface material composition.
 34. The solidsurface material composition of claim 32 wherein said at least oneacrylic monomer is present in the range of from about 20 to 200 parts byweight, based on the total solid surface material composition.
 35. Thesolid surface material composition of claim 32 wherein said granite mixis present in the range of from about 100 to about 500 parts by weight,based on the total solid surface material composition.
 36. A method ofmaking a polyol prepolymer chain extender for silicone modified epoxyand acrylic resins comprising: combining an adduct of at least one amineselected from the group consisting of primary aliphatic amines, primarycycloaliphatic amines, secondary aliphatic amines, and mixtures thereof,with at least one epoxy functional silicone to form a solution; andreacting said solution to form a polyol prepolymer chain extender,wherein said reacting comprises heating said solution at a temperaturein the range of from 130° F. to 210° F. for a time period of from 1 hourto 24 hours.
 37. The method of claim 36 wherein said epoxy functionalsilicone is a silicone modified epoxy resin.
 38. A method of making asilicone modified epoxy resin comprising: combining an adduct of atleast one amine selected from the group consisting of primary aliphaticamines, primary cycloaliphatic amines, secondary aliphatic amines,primary aromatic amines, and secondary aromatic amines, and mixturesthereof, with at least one epoxy functional silicone to form a solution;reacting said solution to form a polyol prepolymer chain extender,wherein said reacting comprises heating said solution at a temperaturein the range of from 130° F. to 210° F. for a time period of from 1 hourto 24 hours; and mixing said polyol prepolymer chain extender with atleast one epoxy resin to form a silicone modified epoxy resin.
 39. Amethod of making a silicone modified acrylic resin comprising: combiningan adduct of at least one amine selected from the group consisting ofprimary aliphatic amines, primary cycloaliphatic amines, secondaryaliphatic amines, primary aromatic amines, and secondary aromaticamines, and mixtures thereof, with at least one epoxy functionalsilicone to form a solution; reacting said solution to form a polyolprepolymer chain extender, wherein said reacting comprises heating saidsolution at a temperature in the range of from 130° F. to 210° F. for atime period of from 1 hour to 24 hours; and mixing said polyolprepolymer chain extender with at least one multi-functional acrylicmonomer to form a silicone modified acrylic resin.